Polyoxyalkylene/unsaturated diester reaction product for cellular foam stabilization

Abstract

Polyoxyalkylene surfactants for cellular foams can be prepared by reacting a polyoxyalkylene adduct and an esterified unsaturated dibasic acid in the presence of a free-radical initiator.

I claim: 
     
       1. A foam material comprising the reaction product of: A. phenol aldehyde resin forming ingredients, and   B. a blowing agent, and   C. a surfactant which comprises the reaction product consisting of (a) a polyoxyalkylene adduct having the formula   H--polyoxyalkylene chain).sub.t R,        wherein R is an organic or inorganic radical and t is the number of polyoxyalkylene chains reacted onto R, and   (b) an esterified unsaturated dibasic acid having the formula   T.sup.1 O.sub.2 C--C.sub.u H.sub.2u-2 --CO.sub.2 T.sup.2        wherein u is 2 or 3 and T 1  and T 2  are identical or different and represent a straight or branched, saturated or unsaturated hydrocarbon chain, in the presence of an effective amount of a free-radical initiator, and wherein polyoxyalkylene adduct is treated either before or after its reaction with the esterified unsaturated dibasic acid with a capping agent capable of reacting with the hydroxyl groups of said adduct to reduce the hydroxyl number of said adduct to less than 50.     
     
     
       2. The composition of claim 1 wherein the esterified unsaturated dibasic acid has the formula   T.sup.1 O.sub.2 C--C.sub.u H.sub.2u-2 --CO.sub.2 T.sup.2     wherein u is 2 or 3 and T 1  and T 2  are identical and represent a straight or branched, saturated or unsaturated hydrocarbon chain of 4 to 18 carbon atoms.   
     
     
       3. The composition of claim 2 wherein the esterified unsaturated dibasic acid is a member selected from the group consisting of dibutyl fumarate, dibutyl maleate, dihexyl maleate, diamyl methylenemalonate, dipropyl itaconate and dibutyl itaconate. 
     
     
       4. The composition of claim 2 wherein T 1  and T 2  represent a straight or branched, saturated or unsaturated hydrocarbon chain of 8 to 18 carbon atoms. 
     
     
       5. The composition of claim 4 wherein the esterified unsaturated dibasic acid is a member selected from the group consisting of dioctyl maleate, ditridecyl maleate and dioleyl maleate. 
     
     
       6. The composition of claim 1 wherein t is an integer from 1 to 8 and the molecular weight of the polyoxyalkylene adduct is above about 1000. 
     
     
       7. The composition of claim 6 wherein the polyoxyalkylene chain or chains of the adduct are derived from an alkylene oxide selected from the group consisting of ethylene oxide, 1,2-epoxypropane, an epoxybutane, and mixtures thereof. 
     
     
       8. The composition of claims 1 or 7 wherein the hydroxyl number of said adduct is reduced to less than 10. 
     
     
       9. The composition of claims 1 or 7 wherein the capping agent is acetic anhydride. 
     
     
       10. The composition of claim 1 wherein an organo transition metal catalyst is additionally present in the free-radical initiated reaction mixture. 
     
     
       11. The composition of claim 1 wherein the esterified unsaturated dibasic acid comprises about 5 to 40 weight percent of the free-radical initiated reaction mixture, and the initiator comprises from about 2 to 30 weight percent, based on the weight of the esterified unsaturated dibasic acid. 
     
     
       12. The composition of claim 11 wherein an organo transition metal catalyst is additionally present in the reaction mixture in a concentration from about 0.001 to 0.05 grams per gram of free-radical initiator. 
     
     
       13. The composition of claim 1 wherein the polyoxyalkylene adduct is a member selected from the group consisting of (a) an alkoxylated amine having the formula: ##STR13##  wherein R 1  is independently an alkoxylated chain having the formula: ##STR14##  s is an integer from 2 to 10 inclusive and the ratio p:q is from 10:90 to 90:10, the molecular weight of said alkoxylated amine being from about 1500 to 12,000,   (b) a linear block copolymer of ethylene oxide and propylene oxide, the molecular weight of said block copolymer being above about 2000 and the ethylene oxide content being from about 30 to 80 weight percent, and   (c) an ethoxylated castor oil.   
     
     
       14. The composition of claim 13 wherein the esterified unsaturated dibasic acid has the formula T 1  O 2  C--C u  H 2u-2  --CO 2  T 2     wherein u is 2 or 3 and T 1  and T 2  are identical and represent a straight or branched, saturated or unsaturated hydrocarbon chain of 8 to 18 carbon atoms.   
     
     
       15. The composition of claim 14 wherein the hydroxyl number of said adduct is reduced to less than 10. 
     
     
       16. The composition of claim 15 wherein the capping agent is acetic anhydride. 
     
     
       17. The composition of claim 16 wherein the esterified unsaturated dibasic acid is a member selected from the group consisting of dioctyl maleate, ditridecyl maleate and dioleyl maleate. 
     
     
       18. The composition of claim 16 wherein (a) the polyoxyalkylene adduct is ethoxylated castor oil, and   (b) the esterified unsaturated dibasic acid is a member selected from the group consisting of dioctyl maleate, ditridecyl maleate and dioleyl maleate.   
     
     
       19. The composition of claim 18 wherein (a) the ethoxylated castor oil contains from about 25 to 60 moles of ethylene oxide per mole of oil, and   (b) the esterified unsaturated dibasic acid is ditridecyl maleate.   
     
     
       20. The composition of claim 19 wherein the ethoxylated castor oil contains from about 35 to 40 moles of ethylene oxide per mole of oil. 
     
     
       21. The composition of claim 20 wherein the ditridecyl maleate comprises about 5 to 40 weight percent of the free-radical initiated reaction mixture and the initiator comprises from about 2 to 30 weight percent, based on the weight of the ditridecyl maleate. 
     
     
       22. In the method of preparing cellular foam from: A. phenol aldehyde resin forming ingredients, and   B. a blowing agent, the improvement which comprises utilizing as surfactant the reaction product consisting of (a) a polyoxyalkylene adduct having the formula   H--polyoxyalkylene chain).sub.t R,        wherein R is an organic or inorganic radical and t is the number of polyoxyalkylene chains reacted onto R, and   (b) an esterified unsaturated dibasic acid having the formula   T.sup.1 O.sub.2 C--C.sub.u H.sub.2u-2 --CO.sub.2 T.sup.2        wherein u is 2 or 3 and T 1  and T 2  are identical or different and represent a straight or branched, saturated or unsaturated hydrocarbon chain, in the presence of an effective amount of a free-radical initiator, and wherein polyoxyalkylene adduct is treated either before or after its reaction with the esterified unsaturated dibasic acid with a capping agent capable of reacting with the hydroxyl groups of said adduct to reduce the hydroxyl number of said adduct to less than 50.     
     
     
       23. The process of claim 22 wherein the esterified unsaturated dibasic acid has the formula   T.sup.1 O.sub.2 C--C.sub.u H.sub.2u-2 --CO.sub.2 T.sup.2     wherein u is 2 or 3 and T 1  and T 2  are identical and represent a straight or branched, saturated or unsaturated hydrocarbon chain of 8 to 18 carbon atoms.   
     
     
       24. The process of claim 23 wherein t is an integer from 1 to 8, the molecular weight of the polyoxyalkylene adduct is above about 1000, and the polyoxyalkylene chain or chains of the adduct are derived from an alkylene oxide selected from the group consisting of ethylene oxide, 1,2-epoxypropane, an epoxybutane, and mixtures thereof. 
     
     
       25. The process of claims 20 or 24 wherein the capping agent is acetic anhydride. 
     
     
       26. The process of claim 22 wherein an organo transition metal catalyst is additionally present during the free-radical initiated reaction. 
     
     
       27. The process of claim 26 wherein the organo transition metal catalyst is ferrocene. 
     
     
       28. The process of claim 22 wherein the esterified unsaturated dibasic acid comprises about 5 to 40 weight percent of the free-radical initiated reaction mixture, and the initiator comprises from about 2 to 30 weight percent, based on the weight of the esterified unsaturated dibasic acid. 
     
     
       29. The process of claim 28 wherein an organo transition metal catalyst is additionally present during the free-radical initiated reaction in a concentration from about 0.001 to 0.05 grams per gram of free-radical initiator. 
     
     
       30. The process of claim 22 wherein the polyoxyalkylene adduct is a member selected from the group consisting of (a) an alkoxylated amine having the formula: ##STR15##  wherein R 1  is independently an alkoxylated chain having the formula: ##STR16##  s is an integer from 2 to 10 inclusive and the ratio p:q is from 10:90 to 90:10, the molecular weight of said alkoxylated amine being from about 1500 to 12,000,   (b) a linear block copolymer of ethylene oxide and propylene oxide, the molecular weight of said block copolymer being above about 2000 and the ethylene oxide content being from about 30 to 80 weight percent, and   (c) an ethoxylated castor oil.   
     
     
       31. The process of claim 30 wherein the esterified unsaturated dibasic acid has the formula   T.sup.1 O.sub.2 C--C.sub.u H.sub.2u-2 --CO.sub.2 T.sup.2     wherein u is 2 or 3 and T 1  and T 2  are identical and represent a straight or branched, saturated or unsaturated hydrocarbon chain of 8 to 18 carbon atoms.   
     
     
       32. The process of claim 31 wherein the capping agent is acetic anhydride, the acetic acid which forms during the capping treatment being removed from the reaction mixture. 
     
     
       33. The process of claim 32 wherein the esterified unsaturated dibasic acid is a member selected from the group consisting of dioctyl maleate, ditridecyl maleate and dioleyl maleate. 
     
     
       34. The process of claim 32 wherein (a) the polyoxyalkylene adduct is ethoxylated castor oil, and   (b) the esterified unsaturated dibasic acid is a member selected from the group consisting of dioctyl maleate, ditridecyl maleate and dioleyl maleate.   
     
     
       35. The process of claim 34 wherein (a) the ethoxylated castor oil contains from about 25 to 60 moles of ethylene oxide per mole of oil, and   (b) the esterified unsaturated dibasic acid is ditridecyl maleate.   
     
     
       36. The process of claim 35 wherein the ethoxylated castor oil contains from about 35 to 40 moles of ethylene oxide per mole of oil. 
     
     
       37. The process of claim 36 wherein the ditridecyl maleate comprises about 5 to 40 weight percent of the free-radical initiated reaction mixture and the initiator comprises from about 2 to 30 weight percent, based on the weight of the ditridecyl maleate.